U.S. patent application number 12/293199 was filed with the patent office on 2009-02-12 for polyphenylene sulfide resin composition, process for producing the same, and molded article.
This patent application is currently assigned to Toray Industries, Inc.. Invention is credited to Atsushi Ishio, Naoya Nakamura, Kei Saitoh.
Application Number | 20090041968 12/293199 |
Document ID | / |
Family ID | 38522414 |
Filed Date | 2009-02-12 |
United States Patent
Application |
20090041968 |
Kind Code |
A1 |
Saitoh; Kei ; et
al. |
February 12, 2009 |
POLYPHENYLENE SULFIDE RESIN COMPOSITION, PROCESS FOR PRODUCING THE
SAME, AND MOLDED ARTICLE
Abstract
A polyphenylene sulfide resin composition including 100 parts by
weight of a resin composition that consists of 99 to 60 wt % of a
polyphenylene sulfide resin (a), and 1 to 40 wt % of at least one
type of noncrystalline resin (b) selected from the group consisting
of polyetherimide resin and polyether sulfone resin and 0.1 to 10
parts by weight of a compound (c) containing at least one group
selected from epoxy group, amino group and isocyanate group,
wherein the non-crystalline resin (b) forms an island phase and the
number-average dispersed particle size of the noncrystalline resin
(b) is 1,000 nm or less.
Inventors: |
Saitoh; Kei; (Negoya-shi,
JP) ; Nakamura; Naoya; (Nagoya-shi, JP) ;
Ishio; Atsushi; (Nagoya-shi, JP) |
Correspondence
Address: |
IP GROUP OF DLA PIPER US LLP
ONE LIBERTY PLACE, 1650 MARKET ST, SUITE 4900
PHILADELPHIA
PA
19103
US
|
Assignee: |
Toray Industries, Inc.
Tokyo
JP
|
Family ID: |
38522414 |
Appl. No.: |
12/293199 |
Filed: |
March 14, 2007 |
PCT Filed: |
March 14, 2007 |
PCT NO: |
PCT/JP2007/055055 |
371 Date: |
September 16, 2008 |
Current U.S.
Class: |
428/36.9 ;
524/500; 525/535 |
Current CPC
Class: |
C08G 75/0213 20130101;
C08K 5/29 20130101; C08L 81/06 20130101; Y10T 428/1352 20150115;
C08G 75/0259 20130101; C08L 81/02 20130101; C08L 81/02 20130101;
B29C 48/29 20190201; C08L 81/06 20130101; B29C 48/37 20190201; B29C
48/40 20190201; Y10T 428/2973 20150115; B29C 48/625 20190201; C08L
79/08 20130101; C08L 79/08 20130101; C08G 75/23 20130101; C08L
81/02 20130101; Y10T 428/139 20150115; C08K 5/1515 20130101; Y10T
428/1397 20150115; C08K 5/17 20130101; C08L 2666/20 20130101; C08L
81/00 20130101; C08L 81/00 20130101; C08L 81/00 20130101 |
Class at
Publication: |
428/36.9 ;
525/535; 524/500 |
International
Class: |
C08L 81/04 20060101
C08L081/04; B32B 1/06 20060101 B32B001/06 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 16, 2006 |
JP |
2006-073532 |
Jul 28, 2006 |
JP |
2006-206190 |
Claims
1-16. (canceled)
17. A polyphenylene sulfide resin composition comprising 100 parts
by weight of a resin composition that consists of 99 to 60 wt % of
a polyphenylene sulfide resin (a), and 1 to 40 wt % of at least one
type of noncrystalline resin (b) selected from the group consisting
of polyetherimide resin and polyether sulfone resin and 0.1 to 10
parts by weight of a compound (c) containing at least one group
selected from epoxy group, amino group and isocyanate group,
wherein the noncrystalline resin (b) forms an island phase and the
number-average dispersed particle size of the noncrystalline resin
(b) is 1,000 nm or less.
18. The polyphenylene sulfide resin composition of claim 17,
wherein compound (c) contains either one or more isocyanate groups
or two or more epoxy groups.
19. The polyphenylene sulfide resin composition of claim 17,
wherein compound (c) is alkoxysilane that contains an isocyanate
group.
20. The polyphenylene sulfide resin composition of claim 17,
wherein noncrystalline resin (b) has a number-average dispersed
particle size of 500 nm or less.
21. The polyphenylene sulfide resin composition of claim 17,
further comprising 0.0001 to 30 parts by weight, relative to the
sum of polyphenylene sulfide resin (a) and noncrystalline resin
(b), of an inorganic filler (d).
22. The polyphenylene sulfide resin composition of claim 17,
wherein polyphenylene sulfide resin (a) has a melt viscosity that
is higher than 80 Pas under conditions of a temperature of
310.degree. C. and a shear velocity of 1000/s.
23. The polyphenylene sulfide resin composition of claim 22,
wherein polyphenylene sulfide resin (a) has a melt viscosity that
is higher than 150 Pas under conditions of a temperature of
310.degree. C. and a shear velocity of 1000/s.
24. The polyphenylene sulfide resin composition of claim 17,
wherein noncrystalline resin (b) is polyetherimide resin.
25. The polyphenylene sulfide resin composition of claim 17,
wherein an amount of lower alcohols with 1 to 4 carbon atoms
generated when pellets of the polyphenylene sulfide resin
composition are thermally melted in a vacuum by heating at
350.degree. C. for 30 minutes is 0.6 mmol % or less relative to the
weight of the polyphenylene sulfide resin composition.
26. The polyphenylene sulfide resin composition of claim 17, having
a tensile elongation (measured by Tensilon UTA2.5T tensile tester
with a chuck distance 64 mm and a tension speed of 10 mm/min) of a
ASTM No. 4 dumbbell-type molded specimen of 80% or more.
27. The polyphenylene sulfide resin composition of claim 17,
wherein the number-average dispersed particle size of
noncrystalline resin (b) in a molded specimen that is prepared by
injection-molding the composition, crushing it and
injection-molding it again is 1,000 nm or less.
28. A method of producing a polyphenylene sulfide resin composition
comprising: adding 0.1 to 10 parts by weight of a compound (c)
containing at least one group selected from the group consisting of
epoxy group, amino group and isocyanate group to 100 parts by
weight of a resin composition that consists of 99 to 60 wt % of a
polyphenylene sulfide resin (a) and 1 to 40 wt % of at least one
type of noncrystalline resin (b) selected from the group consisting
of polyetherimide resin and polyether sulfone resin; melt-kneading
the resulting mixture; and melt-kneading the resulting melt-kneaded
composition one or more times.
29. A method of producing a polyphenylene sulfide resin composition
comprising: adding 0.1 to 10 parts by weight of a compound (c)
containing at least one group selected from the group consisting of
epoxy group, amino group and isocyanate group to 100 parts by
weight of a resin composition that consists of 99 to 60 wt % of a
polyphenylene sulfide resin (a) and 1 to 40 wt % of at least one
type of noncrystalline resin (b) selected from the group consisting
of polyetherimide resin and polyether sulfone resin; melt-kneading
the resulting mixture; and adding 0.02 parts or more of water to
polyphenylene sulfide resin (a) and noncrystalline resin (b) during
the melting-kneading.
30. The method of claim 28, wherein 0.02 parts by weight or more of
water is added to polyphenylene sulfide resin (a) and
noncrystalline resin (b) during the melt-kneading repeated one or
more times after first implementing the melt-kneading.
31. A molded product produced from a polyphenylene sulfide resin
composition as claimed in claim 17.
32. The molded product as claimed in claim 31, wherein the molded
product is a film, sheet or tube.
Description
RELATED APPLICATIONS
[0001] This is a .sctn.371 of International Application No.
PCT/JP2007/055055, with an international filing date of Mar. 14,
2007 (WO 2007/108384 A1, published Sep. 27, 2007), which is based
on Japanese Patent Application Nos. 2006-073532, filed Mar. 16,
2006, and 2006-206190, filed Jul. 28, 2006.
TECHNICAL FIELD
[0002] This disclosure relates to a polyphenylene sulfide resin
composition that is very high in toughness, low in gas emission
during thermal melting and high in processability, and also relates
to a production process therefor and moldings thereof.
BACKGROUND
[0003] Polyphenylene sulfide (hereinafter also referred to as
"PPS") resins have good characteristics as engineering plastics
including high heat resistance, good barrier properties, high
chemical resistance, good electrical insulating properties, and
high moist heat resistance, and therefore they have been widely
used, mainly in the form of injection moldings and extrusions, as
material for different electrical/electronic parts, mechanical
parts and automobile components. PPS resins, however, are generally
lower in toughness than other engineering plastics such as nylon
and PBT, which restricts its uses, and their improvement is now
strongly called for.
[0004] Studies have been carried out on compositions consisting of
a PPS resin and a polyetherimide (hereinafter also referred to as
"PEI") resin or a polyether sulfone (hereinafter also referred to
as "PES") resin. For instance, JP-HEI-4-130158 (claims) has
disclosed a resin composition consisting of a polyarylene sulfide
resin, PEI resin, and organic silane compound. This document,
however, contains no description that suggests the possibility to
achieve a high toughness by using a fine dispersion of a PEI resin.
Moreover, it does not address the volume of alcohols that can
generate from an organic silane compound when such a resin
composition as above is thermally melted. JP-HEI-5-86293 (claims)
has disclosed a resin composition consisting of a PPS resin, PEI
resin, and a silane coupling agent containing one amino or epoxy
group, but gives no description on the possibility of achieving a
high toughness by finely dispersing the PEI resin. Moreover, it
does not address the volume of alcohols that can generate from a
silane coupling agent when such a resin composition as above is
thermally melted. JP 2001-261959 (claims) has disclosed a biaxially
orientated film with high dielectric strength and good electric
characteristics that is produced from a resin composition of PPS
and PEI. JP 2001-261959, however, has no description on the
addition of a compound that contains at least one of the epoxy
group, amino group, and isocyanate group. It gives no description
on the possibility of achieving a high toughness by fine dispersion
of the PEI resin. Moreover, it does not address the volume of
alcohols that can generate from thermal melting. JP 2003-268236
(claims) has disclosed a resin composition consisting of a
polyarylene sulfide resin, PEI or PES resin, and graphite, and in a
detailed description of the invention, addresses the addition of an
alkoxysilane compound containing an isocyanate group. However, any
embodiment given in the document contains a description on an
alkoxysilane compound containing such an isocyanate group as above,
and its effect has not been known. Further, no description is given
on the possibility of achieving a high toughness by fine dispersion
of the PEI resin. No description is given, moreover, on the volume
of alcohols that can generate from an alkoxysilane compound when
such a resin composition as above is thermally melted. JP
2003-147200 (claims) has disclosed a resin composition consisting
of a polyarylene sulfide resin, PEI resin, carbon black,
non-carbon-black non-fiber filler, and fiber filler, and the
detailed description of the invention mentions the addition of an
alkoxysilane compound that contains an isocyanate group. The
embodiments in JP 2003-147200 contain no description on an
alkoxysilane compound that contains such an isocyanate group as
above, and its effect has not been known. Further, no description
is given on the possibility of achieving a high toughness by fine
dispersion of the PEI resin. No description is given, moreover, on
the volume of alcohols that can generate from an alkoxysilane
compound when such a resin composition as above is thermally
melted. WO 2006/051658 (claims), which was published after the
priority date of this disclosure, discloses a biaxially orientated
polyarylene sulfide film with an improved tensile elongation that
is produced from PPS and a PEI or PES resin composition, and the
addition of an alkoxysilane compound containing an isocyanate group
is referred to in a paragraph for detailed description of the
invention. No description is given, however, about the volume of
alcohols that can generate from the alkoxysilane compound when such
a resin composition is thermally melted.
[0005] Thus, no document except WO 2006/051658, which was published
after the priority date of this disclosure, addresses the
possibility that a resin composition with a high tensile elongation
(toughness) can be produced from PPS resin containing finely
dispersed PEI or PES resin with a number-average dispersed particle
size of 1000 nm or less. The above-mentioned documents do not
disclose the volume of alcohols that can generate from the
alkoxysilane compound when such a resin composition is thermally
melted.
[0006] It could therefore be helpful to provide a polyphenylene
sulfide resin composition that is very high in toughness, low in
gas emission during thermal melting and high in processability.
SUMMARY
[0007] We discovered that it is helpful to use a compound
containing one or more groups selected from epoxy group, amino
group and isocyanate group, which is referred to as compound (c),
and finely dispersing PEI or PES resin with a number-average
dispersed particle size of 1000 nm or less, which is referred to as
resin (b), in a PPS, which is referred to as resin (a).
[0008] We thus provide: [0009] 1. A polyphenylene sulfide resin
composition comprising 100 parts by weight of a resin composition
that consists of a polyphenylene sulfide resin, which is referred
to as resin (a), accounting for 99 to 60 wt % and at least one type
of noncrystalline resin selected from polyetherimide resin and
polyether sulfone resin, which is referred to as resin (b),
accounting for 1 to 40 wt %, the sum of the resin (a) and the resin
(b) accounting for 100 wt %, to which 0.1 to 10 parts by weight of
a compound containing at least one group selected from epoxy group,
amino group and isocyanate group, which is referred to as compound
(c), is added, wherein the morphology is characterized in that said
noncrystalline resin (b) forms an island phase, the number-average
dispersed particle size of said noncrystalline resin (b) being
1,000 nm or less, [0010] 2. A production method for a polyphenylene
sulfide resin composition comprising 100 parts by weight of a resin
composition that consists of a polyphenylene sulfide resin, which
is referred to as resin (a), accounting for 99 to 60 wt % and at
least one type of noncrystalline resin selected from polyetherimide
resin and polyether sulfone resin, which is referred to as resin
(b), accounting for 1 to 40 wt %, the sum of the resin (a) and the
resin (b) accounting for 100 wt %, to which 0.1 to 10 parts by
weight of a compound containing at least one group selected from
epoxy group, amino group and isocyanate group, which is referred to
as resin (c), is added, wherein a melt-kneading process is carried
out, followed by repeating the melt-kneading process one or more
times, [0011] 3. A production method for a polyphenylene sulfide
resin composition comprising 100 parts by weight of a resin
composition that consists of a polyphenylene sulfide resin, which
is referred to as resin (a), accounting for 99 to 60 wt % and at
least one type of noncrystalline resin selected from polyetherimide
resin and polyether sulfone resin, which is referred to as resin
(b), accounting for 1 to 40 wt %, the sum of the resin (a) and the
resin (b) accounting for 100 wt %, to which 0.1 to 10 parts by
weight of a compound containing at least one group selected from
epoxy group, amino group and isocyanate group, which is referred to
as compound (c), is added, wherein 0.02 parts or more of water is
added to said polyphenylene sulfide resin (a) and said
noncrystalline resin (b), which in total account for 100 parts by
weight, during the melting-kneading process, and [0012] 4. Moldings
produced from a polyphenylene sulfide resin composition of 1
above.
DETAILED DESCRIPTION
[0013] We provide a description of our compositions, processes and
articles below, including representative examples.
(a) PPS Resin
[0014] The PPS resin (a) is a polymer comprising a repeating unit
as represented by the following structural formula (I):
##STR00001##
and the polymer should preferably comprise a polymer containing a
repeating unit as represented by the above structural formula up to
70 mol % or more, more preferably up to 90 mol % or more to achieve
required heat resistance. In the PPS resin (a), less than 30 mol %
of the total repeating units may comprise repeating units having a
structure as shown below:
##STR00002##
[0015] A PPS copolymer partly comprising such a structure has a
lower melting point, and therefore, such a resin composition is
preferred. There are no specific limitations on the melt viscosity
of the PPS resin (a) used in the invention, but a higher melt
viscosity is generally preferred to achieve a higher toughness.
Typically, it should preferably be more than 80 Pas (310.degree.
C., shear velocity 1000/s), more preferably 100 Pas or more, and
still more preferably 150 Pas or more. With respect to its maximum,
it should preferably be 600 Pas or less to allow the melt to
maintain a required flowability.
[0016] The melt viscosity is measured by a capillograph
manufactured by Toyo Seiki Seisaku-sho, Ltd., under the conditions
of a temperature of 310.degree. C. and a shear velocity of
1000/s.
[0017] A process for producing the PPS resin (a) is described
below, although other processes than that illustrated below may
also be used as along as the PPS resin (a) having the structure
given above can be produced.
[0018] First, the polyhalogenated aromatic compound, sulfidizing
agent, polymerization solvent, molecular weight modifier,
polymerization assistant and polymerization stabilizer used for the
production process are described below.
[Polyhalogenated Aromatic Compound]
[0019] A polyhalogenated aromatic compound contains two or more
halogen atoms in its molecule. Specifically, useful polyhalogenated
aromatic compounds include p-dichlorobenzene, m-dichlorobenzene,
o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene,
1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene,
2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, and
1-methoxy-2,5-dichlorobenzene, of which p-dichlorobenzene is
preferred. A copolymer of two or more different polyhalogenated
aromatic compounds may be used, but such a copolymer should
preferably comprise a p-dihalogenated aromatic compound as primary
component.
[0020] To obtain a PPS resin (a) with a preferred viscosity for
processing, the content of such a polyhalogenated aromatic compound
should typically be in the range of 0.9 to 2.0 moles, more
preferably 0.95 to 1.5 moles, and still more preferably 1.005 to
1.2 moles, per mole of the sulfidizing agent.
[Sulfidizing Agent]
[0021] Useful sulfidizing agents include alkali metal sulfide,
alkali metal hydrosulfide, and hydrogen sulfide.
[0022] Specifically, useful alkali metal sulfides include, for
instance, lithium sulfide, sodium sulfide, potassium sulfide,
rubidium sulfide, cesium sulfide, and mixtures of two or more of
them, of which sodium sulfide is preferred. These alkali metal
sulfides may be used in the form of a hydrate, aqueous mixture or
anhydride.
[0023] Specifically, useful alkali metal hydrosulfides include, for
instance, sodium hydrosulfide, potassium hydrosulfide, lithium
hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and
mixtures of two or more of them, of which sodium hydrosulfide is
preferred. These alkali metal hydrosulfides may be used in the form
of a hydrate, aqueous mixture or anhydride.
[0024] An alkali metal sulfide prepared in situ in the reaction
system from an alkali metal hydrosulfide and an alkali metal
hydroxide may also be used. An alkali metal sulfide prepared first
from an alkali metal hydrosulfide and an alkali metal hydroxide may
be transferred into the polymerization tank before use.
[0025] Instead of this, an alkali metal sulfide prepared in situ in
the reaction system from an alkali metal hydroxide, such as lithium
hydroxide and sodium hydroxide, and a hydrogen sulfide may be used.
An alkali metal sulfide prepared first from an alkali metal
hydroxide, such as lithium hydroxide and sodium hydroxide, and a
hydrogen sulfide may be transferred into the polymerization tank
before use.
[0026] If a loss of part of the sulfidizing agent is caused by
dehydration or other such processes before the start of the
reaction, the loss is subtracted from the volume of the sulfidizing
agent fed to determine its volume actually used.
[0027] The sulfidizing agent may be used in combination with an
alkali metal hydroxide and/or alkaline earth metal hydroxide.
Specifically, preferred alkali metal hydroxides include, for
instance, sodium hydroxide, potassium hydroxide, lithium hydroxide,
rubidium hydroxide, cesium hydroxide, and mixtures of two or more
of them, while useful alkaline earth metal hydroxides include, for
instance, calcium hydroxide, strontium hydroxide, barium hydroxide,
of which sodium hydroxide is preferred.
[0028] If an alkali metal hydrosulfide is used as sulfidizing
agent, an alkali metal hydroxide should preferably be used in
combination with a content in the range of 0.95 to 1.20 moles, more
preferably 1.00 to 1.15 moles, and still more preferably 1.005 to
1.100 moles, per mole of the alkali metal hydrosulfide.
[Polymerization Solvent]
[0029] The polymerization solvent should preferably be an organic
polarity solvent. Specifically, such solvents include N-alkyl
pyrolidone such as N-methyl-2-pyrolidone and N-ethyl-2-pyrolidone;
caprolactams such as N-methyl-.di-elect cons.-caprolactam; aprotic
organic solvents such as 1,3-dimethyl-2-imidazolidinone,
N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric
triamide, dimethyl sulfone, and tetramethylene sulfoxide; and
mixtures of them; all of which are used preferably because they can
react very stably. Of these, methyl-2-pyrolidone (hereinafter also
referred to as NMP) is used particularly preferred.
[0030] The content of the organic polarity solvent should
preferably be in the range of 2.0 to 10 moles, more preferably 2.25
to 6.0 moles, and still more preferably 2.5 to 5.5 moles, per mole
of the sulfidizing agent.
[Molecular Weight Modifier]
[0031] A monohalogen compound (not necessarily an aromatic
compound) may be used in combination with the above polyhalogenated
aromatic compound in order to form ends in the resulting PPS resin
(a) or to adjust its polymerization reaction and molecular
weight.
[Polymerization Assistant]
[0032] The use of a polymerization assistant is helpful for quick
production of a PPS resin (a) with a relatively high polymerization
degree. The above-mentioned polymerization assistant is a substance
that can serve to produce a PPS resin (a) with an increased
viscosity. Specifically, such polymerization assistants include,
for instance, organic carboxylate, water, alkali metal chloride,
organic sulfonate, alkali metal sulfate, alkaline earth metal
oxide, alkali metal phosphate, and alkaline earth metal phosphate.
They may be used singly, or two or more of them may be used in
combination. Among others, organic carboxylate, water, and alkali
metal chloride are preferred, alkali metal carboxylate and lithium
chloride being preferred as said organic carboxylate and alkali
metal chloride, respectively.
[0033] The above alkali metal carboxylate is a compound that is
represented by the following general formula: R(COOM).sub.n (where
R denotes an alkyl group with 1 to 20 carbons, cycloalkyl group,
aryl group, alkyl aryl group, or aryl alkyl group, M denoting an
alkali metal selected from lithium, sodium, potassium, rubidium and
cesium, and n denoting an integer in the range of 1 to 3). The
alkali metal carboxylate to be used may be in the from of a
hydrate, anhydride, or aqueous solution. Specifically, useful
alkali metal carboxylates include, for instance, lithium acetate,
sodium acetate, potassium acetate, sodium propionate, lithium
valerate, sodium benzoate, sodium phenylacetate, p-potassium
toluate, and mixtures of them.
[0034] The alkali metal carboxylate may be produced by adding about
the same chemical equivalents of an organic acid and one or more
compound selected from alkali metal hydroxide, alkali metal
carbonate, and alkali metal bicarbonate, and allowing them to
react. Of such alkali metal carboxylates, lithium salts are
expensive though it is high in solubility in the reaction system
and can have a high assistant effect, while potassium, rubidium and
cesium salts is not sufficiently high in solubility in the reaction
system. Thus, sodium acetate is used most preferably because of its
moderately high solubility in the polymerization system.
[0035] When used as polymerization assistant, the content of these
alkali metal carboxylates should typically be in the range of 0.01
to 2 moles per mole of the alkali metal sulfide used, and it should
preferably be in the range of 0.1 to 0.6 moles, still more
preferably 0.2 to 0.5 moles, to achieve a higher polymerization
degree.
[0036] When water is used as polymerization assistant, its content
should typically be in the range of 0.3 to 15 moles per mole of the
alkali metal sulfide used, and it should preferably be in the range
of 0.6 to 10 moles, still more preferably 1 to 5 moles, to achieve
a higher polymerization degree.
[0037] As a matter of course, two or more of these polymerization
assistant may be used in combination, and for instance, the
combined use of an alkali metal carboxylate and water allows a
higher molecular weight to be achieved in a smaller amount than
that required when they are used singly.
[0038] There are no specific limitations on the timing of the
addition of these polymerization assistants, and they may be added
during the preprocessing step that is described later, at the start
of polymerization, or during the polymerization step. They may be
added in lots, but when an alkali metal carboxylate is used as
polymerization assistant, it should preferably be added in one lot
at the start of the preprocessing step or at the start of the
polymerization step because of easy addition operations. If water
is used as polymerization assistant, good effects are achieved by
adding it during the polymerization step that is performed after
the feeding of a polyhalogenated aromatic compound.
[Polymerization Stabilizer]
[0039] A polymerization stabilizer may be used to stabilize the
polymerization reaction system and prevent side reactions. A
polymerization stabilizer contributes to the stabilization of the
polymerization reaction system and suppresses undesired side
reactions. One of the signs of side reactions is the production of
thiophenol, and the addition of a polymerization stabilizer can
serve to control the production of thiophenol. Specifically, useful
polymerization stabilizers include alkali metal hydroxide, alkali
metal carbonate, alkaline earth metal hydroxide, and alkaline earth
metal carbonate. Of these, alkali metal hydroxides such as sodium
hydroxide, potassium hydroxide, and lithium hydroxide are
preferred. The above-mentioned alkali metal carboxylates can be
regarded as polymerization stabilizers because they can stabilize
the polymerization process. When an alkali metal hydrosulfide is
used as sulfidizing agent, the combined use with an alkali metal
hydroxide is particularly preferable as described above. Here, the
surplus alkali metal hydroxide relative to the amount of the
sulfidizing agent can act as polymerization stabilizer. Such
polymerization stabilizer may be used singly, or two or more of
them may be used in combination.
[0040] The polymerization stabilizer used should typically be in
the range of 0.02 to 0.2 moles, more preferably 0.03 to 0.1 moles,
and still more preferably 0.04 to 0.09 moles, per mole of the
alkali metal sulfide fed. A required stabilization effect will not
be achieved if the content is too low, whereas its addition in an
excessive amount will be economically disadvantageous and lead to a
lower polymer yield.
[0041] There are no specific limitations on the timing of the
addition of these polymerization stabilizers, and they may be added
during the preprocessing step that is described later, at the start
of polymerization, or during the polymerization step. They may be
added in lots, they should preferably be added in one lot at the
start of the preprocessing step or at the start of the
polymerization step because of easy operations.
[0042] Next, preferred production processes for the PPS resin (a)
are described concretely, focusing sequentially on the
preprocessing step, polymerization reaction step, recovery step,
and post-processing step, though, as a matter of course, this
disclosure is not limited by this description.
[Preprocessing Step]
[0043] In producing the PPS resin (a), the sulfidizing agent is
usually used in the form of a hydrate, but preferably, a mixture of
an organic polarity solvent and a sulfidizing agent is heated
before adding a polyhalogenated aromatic compound to remove excess
water out of the system.
[0044] As stated previously, a sulfidizing agent may be prepared
from an alkali metal hydrosulfide and an alkali metal hydroxide in
situ in the reaction system or in a separate tank other than the
polymerization tank. There are no specific limitations on this
process, but preferably, an alkali metal hydrosulfide and an alkali
metal hydroxide are added to an organic polarity solvent in an
inert gas atmosphere in the temperature range of room temperature
to 150.degree. C., preferably room temperature to 100.degree. C.
and heated under atmospheric pressure or reduced pressure up to at
least 150.degree. C. or more, preferably up to 180 to 260.degree.
C., to evaporate water. A polymerization assistant may be added at
this stage. Toluene or other compounds may be added to this
reaction to promote the evaporation of water.
[0045] The volume of water in the polymerization system for the
polymerization reaction should preferably be in the range of 0.3 to
10.0 moles per mole of the sulfidizing agent fed. The volume of
water in the polymerization system is calculated by subtracting the
volume of water removed out of the polymerization system from the
total volume of water fed to the polymerization system. Such water
to be fed may be in the form of water, aqueous solutions, or water
of crystallization.
[Polymerization Reaction Step]
[0046] To produce the PPS resin (a), a polyhalogenated aromatic
compound is reacted with a sulfidizing agent in an organic polarity
solvent in the temperature range of 200.degree. C. to 290.degree.
C.
[0047] To start the polymerization reaction step, the organic
polarity solvent, the sulfidizing agent and the polyhalogenated
aromatic compound are mixed preferably in an inert gas atmosphere
preferably in the temperature range of room temperature to
240.degree. C., more preferably 100 to 230.degree. C. A
polymerization assistant may be added at this stage. These
substances may be added either in random order or at a time.
[0048] Such a mixture is heated typically up to the temperature
range of 200.degree. C. to 290.degree. C. There are no specific
limitations on the heating rate, but heating is performed typically
in the range of 0.01 to 5.degree. C. per minute, and preferably in
the range of 0.1 to 3.degree. C. per minute.
[0049] Typically, the mixture is heated up to a final temperature
of 250 to 290.degree. C., and allowed to react typically for 0.25
to 50 hours, preferably 0.5 to 20 hours, at the temperature.
[0050] As an effective way of achieving a higher polymerization
degree, the reaction may be maintained for a certain period at, for
instance, 200 to 260.degree. C. at a stage before the final
temperature is reached, followed by heating up to 270 to
290.degree. C.
[0051] The time period for the reaction at 200 to 260.degree. C. is
typically in the range of 0.25 to 20 hours, and preferably 0.25 to
10 hours.
[0052] The polymerization may be carried out in several stages to
produce a polymer with a higher polymerization degree. An effective
way of carrying out the polymerization in several stages, such
stages may be performed above a conversion degree of the
polyhalogenated aromatic compound of 40 mol %, preferably 60 mol %,
in a system at 245.degree. C.
[0053] The conversion degree of the polyhalogenated aromatic
compound (referred to as PHA) is calculated by the following
equation. The PHA residue can be determined typically by gas
chromatography.
(A) In cases where the polyhalogenated aromatic compound is added
in an excessive amount in terms of molar ratio relative to the
alkali metal sulfide:
Conversion degree=[PHA feed (moles)-PHA residue (moles)]/[PHA feed
(moles)-PHA excess (moles)]
(B) In cases other than (A):
Conversion degree=[PHA feed (moles)-PHA residue (moles)]/[PHA feed
(moles)]
[Recovery Step]
[0054] In the production process for the PPS resin (a), solid
material is recovered from the polymerization liquid, which
contains polymers and solvents, after the completion of the
polymerization. Any known recovery method may be used to recover
the PPS resin (a).
[0055] For instance, the reaction liquid may be gradually cooled
after the completion of the polymerization, followed by recovery of
polymer particles. There are no specific limitations on the rate of
the gradual cooling, but it is typically about 0.1 to 3.degree. C.
per minute. It is not necessary to cool the liquid at a constant
rate over the entire cooling step, but cooling may be performed at
a rate of, for instance, 0.1 to 1.degree. C. per minute before the
start of crystal deposition, and at 1.degree. C. or more per minute
subsequently.
[0056] Quenching the liquid followed by recovery is also a
preferable method, and flushing is a preferred way of performing
this recovery method. Specifically, the polymerization reaction
liquid maintained under high-temperature, high-pressure conditions
(typically at 250.degree. C. or more, 8 kg/cm.sup.2 or more) is
allowed to spout into an atmosphere under atmospheric pressure or
reduced pressure, so that the polymer is recovery as particles
while the solvent is recovered at the same time. The term flushing
means allowing the polymerization liquid to spout through a nozzle.
The atmosphere for such flushing may be, for instance, a nitrogen
or steam atmosphere under atmospheric pressure, and its temperature
is typically in the range of 150 to 250.degree. C.
[Post-Processing Step]
[0057] The PPS resin (a) resulting from the above polymerization
and recovery steps may be subjected to acid treatment, hot-water
treatment or cleaning with an organic solvent.
[0058] Acid treatment to be performed may be as follows. There are
no specific limitations on the acid to be used for the acid
treatment of the PPS resin (a), unless it can act to decompose the
PPS resin (a). Useful acids include acetic acid, hydrochloric acid,
sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and
propyl acid, of which acetic acid and hydrochloric acid are
preferred. Acids such as nitric acid that can decompose or degrade
the PPS resin (a) are not preferred.
[0059] For such acid treatment, the PPS resin (a) may be immersed
in an acid or aqueous acid solution, and the liquid may be stirred
or heated as required. If acetic acid is used, for instance, good
effect is achieved by immersing powder of the PPS resin in an
aqueous solution with a pH of 4 heated at 80 to 200.degree. C. and
stirred for 30 minutes. The solution after the treatment may have a
pH of above 4, or for instance in the range of 4 to 8. The PPS
resin (a) subjected to acid treatment should preferably be washed
several times in water or hot water to remove the remaining acids
and salts. The water to be used for the washing should preferably
be distilled water or deionized water in order to prevent the
preferred chemical alteration of the PPS resin (a) achieved by acid
treatment from being injured.
[0060] Hot-water treatment should be carried out as follows. During
the hot-water treatment of the PPS resin (a), the temperature of
the hot water should preferably be 100.degree. C. or more, more
preferably 120.degree. C. or more, still more preferably
150.degree. C. or more, and still more preferably 170.degree. C. or
more. A temperature of lower than 100.degree. C. is not preferred
because the preferred chemical alteration of PPS resin (a) will not
be achieved to a required degree.
[0061] To achieve the preferred chemical alteration of the PPS
resin (a), the water to be used for the hot water washing should
preferably be distilled water or deionized water. There are no
specific limitations on the operations of the hot-water treatment,
and the treatment may be carried out by, for instance, pouring a
required volume of the PPS resin (a) in a required volume of water,
followed by heating and stirring in a pressure vessel, or by
continuous implementation of the hot-water treatment. With respect
to the proportion between the PPS resin (a) and water, the volume
of water should preferably be larger, and a bath ratio of 200 g or
less of the PPS resin (a) to one liter of water is preferred.
[0062] With respect to the atmosphere for the treatment, an inert
atmosphere is preferred in order to avoid the decomposition of the
end groups, which is not desirable. Furthermore, it is preferred
that the PPS resin (a) after the hot-water treatment should
preferably be washed in warm water to remove residual matters.
[0063] Washing with an organic solvent is performed as follows.
There are no specific limitations on the organic solvent to be used
for the washing of the PPS resin (a) unless it will act to
decompose the PPS resin (a), and useful ones include, for instance,
nitrogen-containing polar solvents such as N-methyl-2-pyrolidone,
dimethyl formamide, dimethyl acetamide, 1,3-dimethyl
imidazolidinone, hexamethylphosphorus amide, and piperazinones;
sulfoxide or sulfone-based solvents such as dimethyl sulfoxide,
dimethyl sulfone, and sulfolane; ketone-based solvent such as
acetone, methyl ethyl ketone, diethyl ketone, and acetophenone;
ether-based solvents such as dimethyl ether, dipropyl ether,
dioxane, and tetrahydrofuran; halogen-based solvents such as
chloroform, methylene chloride, trichloroethylene, ethylene
dichloride, perchloroethylene, monochloroethane, dichloroethane,
tetrachloroethane, perchloroethane, and chlorobenzene; alcohols and
phenol-based solvents such as methanol, ethanol, propanol, butanol,
pentanol, ethylene glycol, propylene glycol, phenol, creosol,
polyethylene glycol, and polypropylene glycol; and aromatic
hydrocarbon-based solvents such as benzene, toluene, and xylene. Of
these organic solvents, N-methyl-2-pyrolidone, acetone, dimethyl
formamide and chloroform are particularly preferred. These organic
solvents, furthermore, may be used singly, or two or more of them
may be used in combination.
[0064] The washing in the organic solvent may be carried out by,
for instance, immersing the PPS resin (a) in the organic solvent,
and stirring or heating may also be performed as required. There
are no specific limitations on the washing temperature for washing
the PPS resin (a) in the organic solvent, and the washing may be
performed in the range of room temperature to about 300.degree. C.
The washing efficiency tends to increase with a washing
temperature, but a sufficient effect of washing can be usually
achieved at a washing temperature in the range of room temperature
to 150.degree. C. The washing can also be performed under pressure
in a pressure vessel at above the boiling point of the organic
solvent. In addition, there are no specific limitations on the
washing time. Depending on the washing conditions, a sufficient
effect is achieved by washing for five minutes or more by batch
washing. Continuous washing is also useful.
[0065] The PPS may contain a salt of an alkaline earth metal such
as Ca. Such an alkaline earth metal salt may be introduced by, for
instance, adding the alkaline earth metal salt before said
preprocessing step, during preprocessing step or after
preprocessing step, by adding an alkaline earth metal salt in the
polymerization tank, before the polymerization step, during
polymerization step or after polymerization step, or by adding an
alkaline earth metal salt at the beginning, in the middle or at the
end of said washing step. Of these, the easiest way is adding the
alkaline earth metal salt after removing residual oligomers and
residual salts by washing in an organic solvent, warm water or hot
water. It is preferred that the alkaline earth metal salt is
introduced in the PPS in the form of an alkaline earth metal ion
such as acetate, hydroxide, and carbonate. The excess alkaline
earth metal salt should preferably be removed by, for instance,
washing in warm water. When the alkaline earth metal ion is
introduced, the content of the alkaline earth metal ion should
preferably be 0.001 mmol or more, more preferably 0.01 mmol or
more, per gram of the PPS. The temperature for this should
preferably be 50.degree. C. or more, more preferably 75.degree. C.
or more, and still more preferably 90.degree. C. or more. There are
no specific limitations on the maximum temperature limit, but a
temperature of 280.degree. C. or lower is usually preferred from
the viewpoint of operability. The bath ratio (weight of washing
fluid relative to that of dry PPS) should preferably be 0.5 or
more, more preferably 3 or more, and still more preferably 5 or
more.
[0066] The molecular weight of the PPS resin (a) may be increased
by performing thermal-oxidation crosslinking treatment such as
heating the material in an oxygen atmosphere after the completion
of the polymerization or heating the material after a crosslinking
such as a peroxide is added.
[0067] If dry heat treatment is performed to increase the molecular
weight by thermal-oxidation crosslinking, the temperature used
should preferably be 160 to 260.degree. C., more preferably 170 to
250.degree. C. The concentration of oxygen should preferably be 5%
by volume or more, more preferably 8% by volume or more. There are
no specific limitations on the upper limit of the oxygen
concentration, but the practical maximum is about 50% by volume.
The treatment time should preferably be in the range of 0.5 to 100
hours, more preferably 1 to 50 hours, and still more preferably 2
to 25 hours. The heat treatment apparatus may be an ordinary hot
air dryer, a rotation type heater, or a heater with a stirring
blade, of which the rotation type heater and the stirring blade
type heater are preferred because they are efficient and can
achieve uniform treatment.
[0068] Dry heat treatment may be performed with the aim of
controlling the thermal-oxidation crosslinking and removing the
volatile matter. The temperature for this should preferably be in
the range of 130 to 250.degree. C., more preferably 160 to
250.degree. C. The oxygen concentration for this should preferably
be less than 5% by volume, more preferably less than 2% by volume.
The treatment time should preferably be in the range of 0.5 to 50
hours, more preferably 1 to 20 hours, and still more preferably 1
to 10 hours. The heat treatment apparatus may be an ordinary hot
air dryer, a rotation type heater, or a heater with a stirring
blade, of which the rotation type heater and the stirring blade
type heater are preferred because they are efficient and can
achieve uniform treatment.
[0069] The PPS resin (a) to be used should preferably be a
virtually straight-chain polymer that is not crosslinked by thermal
oxidation with the aim of increasing the molecular weight to
achieve a required toughness. Useful materials as the PPS resin (a)
for the invention include Toray Industries M2588, M2888, M2088,
T1881, L2120, L2480, M2100, M2900, E2080, E2180, and E2280.
(b) Polyetherimide Resin and Polyether Sulfone Resin
[0070] As the noncrystalline resin, at least one selected from
polyetherimide resins and polyether sulfone resins is used as
described previously, but use of polyetherimide resins is preferred
because a small amount of them can be effective to achieve a high
toughness. For the polyetherimides, there are no specific
limitations if they are polymers that consist of aliphatic,
alicyclic or aromatic ether units and cyclic imide groups as
repeating units and can be melt-processed. Their polyetherimide
backbone chain may contains structural units other than cyclic
imide or ether bonds, such as aromatic, aliphatic or alicyclic
ester units and oxycarbonyl units, unless they have adverse
influence of the effect of the invention.
[0071] Specifically, preferred polyetherimides are those polymers
which are represented by the following general formula:
##STR00003##
where R.sub.1 represents a divalent aromatic residue containing 6
to 30 carbon atoms, R.sub.2 a divalent organic group selected from
aromatic residues containing 6 to 30 carbon atoms, alkylene groups
containing 2 to 20 carbon atoms, cycloalkylene groups containing 2
to 20 carbon atoms, and polydiorganosiloxane groups containing 2 to
8 carbon atoms and chain-stopped with alkylene groups. As the above
R.sub.1 and R.sub.2, units comprising an aromatic residue as
represented by the following formulae, for instance, are
preferred.
##STR00004##
[0072] For the present invention, a condensation product of a
2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride
comprising structural units as represented by the following
formulae and either a m-phenylene diamine or a p-phenylene diamine
is preferred from the viewpoint of melting moldability and required
costs. Such polyetherimides are commercially available from General
Electric Company under the brand name of Ultem.
##STR00005##
[0073] The polyether sulfone used in the invention is a resin
comprising repeating backbone units that contain a sulfone bond and
an ether bond.
##STR00006##
[0074] These compounds are commercially available under the brand
name of Victrex PES or Sumikaexcel.
(c) a Compound Comprising One or More of Epoxy Group, Amino Group,
and Isocyanate Group
[0075] It is necessary to add a compound comprising one or more of
epoxy group, amino group, and isocyanate group, which is referred
to as compound (c), that acts as compatibility improver with the
aim of stably maintaining a high toughness.
[0076] Useful epoxy-containing compounds include glycidyl ethers of
a bisphenol such as bisphenol A, resorcinol, hydroquinone,
pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene,
bisphenol S, trihydroxydiphenyl dimethyl methane,
4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol,
and 2,2,5,5-tetrakis(4-hydroxyphenyl)hexane, those comprising a
halogenated bisphenol instead of a bisphenol as listed above,
glycidyl ether based epoxy compounds such as diglycidyl ether
comprising a butanediol, glycidyl ester based compounds such as
glycidyl phthalate, glycidyl epoxy resins such as glycidyl amine
based compounds comprising N-glycidyl aniline etc., linear epoxy
compounds such as epoxidized polyolefine and epoxidized soybean
oil, and cyclic non-glycidyl epoxy resins such as viryl cyclohexene
dioxide and dicyclopentadiene dioxide.
[0077] In addition, novolac-type epoxy resins can also be useful.
Novolac-type epoxy resin comprises two or more epoxy groups and is
produced typically by allowing novolac-type phenol resin to react
with epichlorohydrin. A novolac-type phenol resin is produced
through condensation reaction of a phenol and formaldehyde. There
are no specific limitations on the phenol to be used as raw
material, and useful ones include phenol, o-creosol, m-creosol,
p-creosol, bisphenol A, resorcinol, p-tertiary butylphenol,
bisphenol F, bisphenol S, and condensation products of them.
[0078] Furthermore, olefin copolymers containing an epoxy group can
also be useful. Such olefin copolymers containing an epoxy group
(epoxy-containing olefin copolymers) include olefin copolymers that
are produced by introducing an epoxy-containing monomer component
into an olefin-based (co)polymer. Copolymers that are produced from
an olefin-based polymer containing a double bond in its backbone
chain by epoxidizing the double bond portion.
[0079] Useful units containing a functional group that serves to
introduce an epoxy-containing monomer component into an
olefin-based (co)polymer include epoxy-containing monomers such as
glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate,
glycidyl itaconate, and glycidyl citraconate.
[0080] There are no specific limitations on the method used to
introduce these epoxy-containing components, and useful ones
include copolymerization with an .alpha.-olefin, and graft
introduction into an olefin (co)polymer using a radical
initiator.
[0081] The content of the epoxy-containing monomer introduced
should preferably be 0.001 to 40 mol %, more preferably 0.01 to 35
mol %, of the total monomers used as raw material to produce the
epoxy-containing olefin-based copolymer.
[0082] Particularly preferred epoxy-containing olefin copolymers
include olefin-based copolymers produced from an .alpha.-olefin and
a glycidyl ester of an .alpha.,.beta.-unsaturated carboxylic acid
as copolymerization units. Such preferred .alpha.-olefins include
ethylene. These copolymers may be further copolymerized with an
.alpha.,.beta.-unsaturated carboxylic acid or its alkyl ester such
as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate,
methacrylic acid, methyl methacrylate, ethyl methacrylate, and
butyl methacrylate, as well as styrene and acrylonitrile.
[0083] These olefin copolymers may be random, alternating, block,
or graft copolymers.
[0084] Of said olefin copolymers produced by copolymerization of an
.alpha.-olefin and a glycidyl ester of an
.alpha.,.beta.-unsaturated carboxylic acid, those comprising 60 to
99 wt % of an .alpha.-olefin and 1 to 40 wt % of an glycidyl ester
of an .alpha.,.beta.-unsaturated carboxylic acid are particularly
preferred.
[0085] Specifically, such glycidyl esters of an
.alpha.,.beta.-unsaturated carboxylic acid include glycidyl
acrylate, glycidyl methacrylate, and glycidyl ethacrylate, of which
glycidyl methacrylate is preferred.
[0086] Useful olefin-based copolymers comprising, as essential
copolymerization components, an .alpha.-olefin and a glycidyl ester
of an .alpha.,.beta.-unsaturated carboxylic acid include
ethylene/propylene-g-glycidyl methacrylate copolymer ("g"
representing "graft," the same applying hereinafter),
ethylene/butene-1-g-methglycidyl acrylate copolymer,
ethylene-glycidyl methacrylate copolymer-g-polystyrene,
ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene
copolymer, ethylene-glycidyl methacrylate copolymer-g-PMMA,
ethylene/glycidyl acrylate copolymer, ethylene/glycidyl
methacrylate copolymer, ethylene/methyl acrylate/glycidyl
methacrylate copolymer, and ethylene/methyl methacrylate/glycidyl
methacrylate copolymer.
[0087] In addition, alkoxysilanes containing an epoxy group are
also useful. Specifically, such compounds include epoxy-containing
alkoxysilane compounds such as .gamma.-glycidoxypropyl
trimethoxysilane, .gamma.-glycidoxypropyl triethoxysilane, and
.beta.-(3,4-epoxy cyclohexyl)ethyl trimethoxysilane.
[0088] Useful amino-containing compounds include amino-containing
alkoxysilanes. Specifically, such compounds include
amino-containing alkoxysilane compounds such as
.gamma.-(2-aminoethyl)aminopropyl methyl dimethoxysilane,
.gamma.-(2-aminoethyl)aminopropyl trimethoxysilane, and
.gamma.-aminopropyl trimethoxysilane.
[0089] Useful compounds containing one or more isocyanate groups
include isocyanate compounds such as 2,4-tolylene diisocyanate,
2,5-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, and
polymethylene polyphenyl polyisocyanate, and isocyanate-containing
alkoxysilane compounds such as .gamma.-isocyanate propyl
triethoxysilane, .gamma.-isocyanate propyl trimethoxysilane,
.gamma.-isocyanate propyl methyl dimethoxysilane,
.gamma.-isocyanate propyl methyl diethoxysilane, .gamma.-isocyanate
propyl ethyl dimethoxysilane, .gamma.-isocyanate propyl ethyl
diethoxysilane, and .gamma.-isocyanate propyl trichlorosilane.
[0090] In particular, the use of at least one compound selected
from the compounds containing one or more isocyanate groups and
compounds containing two or more epoxy groups is preferred to
stably maintaining a high toughness, and alkoxysilanes containing
an isocyanate group are more preferred.
[0091] The mix proportion of the PPS resin (a) and the
polyetherimide resin and/or polyether sulfone resin (b) should
preferably be in the range of (a)/(b)=99 to 60 wt %/1 to 40 wt %,
more preferably (a)/(b)=97 to 70 wt %/2 to 30 wt %, and still more
preferably (a)/(b)=95 to 80 wt %/2 to 20 wt %, the sum of (a) and
(b) accounting for 100 wt %. A sufficiently high toughness will not
be achieved if the PPS resin (a) accounts for more than 99 wt %,
and the melt flowability will be too low if the PPS resin (a)
accounts for less than 60 wt %.
[0092] The content of the component (c) should preferably be in the
range of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts
by weight, still more preferably 0.2 to 3 parts by weight, relative
to the sum of the polyphenylene sulfide resin (a) and the
noncrystalline resin (b) that accounts for 100 parts by weight. A
sufficiently high toughness will not be maintained stably if the
component (c) accounts for less than 0.05 parts by weight, and the
melt flowability will be too low if the component (c) accounts for
more than 10 parts by weight.
[0093] The PPS resin composition has a high toughness in addition
to the excellent heat resistance, chemical resistance, and barrier
properties that the PPS resin (a) originally possesses. For such
characteristics to develop, it should have such a morphological
feature that the PPS resin (a) forms a sea phase (continuous phase
or matrix) while the polyetherimide resin and/or polyether sulfone
resin (b) form an island phase (dispersed phase). It is essential,
furthermore, for the polyetherimide resin and/or polyether sulfone
resin (b) to have a number-average dispersed particle size of 1000
nm or less, preferably 700 nm or less, and more preferably 500 nm
or less. Its minimum should preferably be 1 nm or more to maintain
a sufficient productivity. The toughness will be too low if the
number-average dispersed particle size of the polyetherimide resin
and/or polyether sulfone resin (b) is more than 1000 nm.
[0094] Even when recycled, the PPS resin composition stably
maintains a high toughness. For such characteristics to develop, it
is preferred that the PPS resin (a) and the polyetherimide resin
and/or polyether sulfone resin (b) maintains a sea phase
(continuous phase or matrix) and an island phase (dispersed phase),
respectively, if fragments of a broken injection-molded product are
injection-molded again. Furthermore, the number-average dispersed
particle size of the polyetherimide resin and/or polyether sulfone
resin (b) should preferably be 1000 nm or less, more preferably 700
nm or less, and still more preferably 500 nm or less. Its minimum
should preferably be 1 nm or more to maintain a sufficient
productivity.
[0095] The number-average dispersed particle size referred to here
is determined as follows: prepare a ASTM No. 4 sample by molding
the PPS resin (a) at a temperature +20.degree. C. above the melting
peak temperature, cut out a specimen of 0.1 .mu.m or less at
-20.degree. C. from the central portion in the cross sectional
direction of the dumbbell sample, observe it at a magnification of
10,000 to 20,000 under a Hitachi, Ltd., H-7100 transmission
electron microscope (resolution (particle image) 0.38 nm,
magnifying power 500,000 to 600,000), select appropriately 100
dispersed phase portions of the polyetherimide resin and/or
polyether sulfone resin (b), measure each portion's maximum and
minimum diameters to determine the average as its dispersed
particle average size, and calculate the average over all portions
to determine the number-average dispersed particle size.
[0096] Such a resin composition comprising an
alkoxysilane-containing compound can release alcohol as a result of
hydrolysis of the alkoxysilane during melt processing. For the PPS
resin composition, the volume of the lower alcohols with 1 to 4
carbon atoms generated during thermal melting in a vacuum at
350.degree. C. for 30 minutes should preferably be 0.6 mmol % or
less, more preferably 0.4 mmol % or less, still more preferably 0.3
mmol % or less, and still more preferably 0.25 mmol % or less,
relative to the weight of the PPS resin composition. By controlling
the alcohol generation at 0.6 mmol % or less, the volume of
volatile constituents generated from molding of film, sheets or
tubes can be decreased to prevent the formation of voids in the
molded material. This, in turn, serves to prevent breakage of the
film and bulging of the molded material that can result from the
voids, thus improving the efficiency of continuous production.
[0097] The volume of generated alcohols is determined as follows:
dry the PPS resin composition by leaving it overnight in a hot air
flow at 130.degree. C., vacuum-encapsulate it in a glass ampule,
heat it in a tubular furnace, and collect it, followed by
measurement. The size of the glass ampule should consists of a body
portion of 100 mm.times.25 mm and a neck portion of 255 mm.times.12
mm, both with a thickness of 1 mm. Specifically, quantitative
determination of the alcohol generation should be carried out as
follows: vacuum-encapsulate 3 g of the PPS resin composition in a
glass ampule, insert only the body portion of the ampule into a
tubular furnace (ceramic tubular electric furnace ARF-30K
manufactured by Asahi Rika Manufacturing) at 350.degree. C., and
heat it for 30 minutes to allow the volatilized gas to be cooled
and liquefied in the neck portion of the ampule that is not heated
by the tubular furnace. The neck portion is cut out and the gas
left is recovered by dissolving it in 4 g of N-methyl-2-pyrolidone
(NMP). Then the NMP solution of the collected gas is separated and
measured by gas chromatography using Shimadzu Corporation GC-14A to
determine the volume of the generated alcohols.
[0098] A preferred method for producing a resin composition that
does not generate a large amount of alcohols is to carrying out a
melting-kneading process using a biaxial extruder has at least two
kneading units, followed by carrying the melting-kneading process
one or more times. When the PPS resin (a) and the PEI resin and/or
PES resin (b) are subjected to the melting-kneading process, it is
also preferred to add 0.02 part by weight or more of water relative
to the total amount of water that accounts for 100 parts by weight.
This method works to accelerate the hydrolysis of the alkoxysilane
compound and serves to further decrease the alcohol generation from
the resulting resin composition. There are no specific limitations
on the way of adding water, but water may be side-fed in the middle
of the extruder using liquid feeding equipment such as gear pump
and plunger pump, or water may be added or side-fed in the middle
of the extruder during the repeated melting-kneading process
following the first melting-kneading process. Other preferred
methods include providing five or more kneading units to increase
the kneading performance and using an extruder with a large
kneading length, and it is not always necessary to repeat the
kneading process two or more times or add water.
(d) Inorganic Filler
[0099] The PPS resin composition may contain an inorganic filler
(d), which is not an essential component, unless it has adverse
influence. Specifically, such inorganic fillers (d) include fibrous
fillers such as glass fiber, carbon fiber, carbon nanotube, carbon
nanohorn, potassium titanate whisker, zinc oxide whisker, calcium
carbonate whisker, walastenite whisker, aluminum borate whisker,
aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber,
asbestos fiber, gypsum fiber, and metal fiber; silicates such as
fullerene, talc, walastenite, zeolite, sericite, mica, kaolin,
clay, pyrophyllite, silica, bentonite, asbestos, and alumina
silicate; metal compounds such as silicon oxide, magnesium oxide,
alumina, zirconium oxide, titanium oxide, and iron oxide;
carbonates such as calcium carbonate, magnesium carbonate, and
dolornite; sulfates such as calcium sulfate and barium sulfate;
hydroxides such as calcium hydroxide, magnesium hydroxide, and
aluminum hydroxide; and non-fibrous fillers such as glass beads,
glass flakes, glass powder, ceramic beads, boron nitride, silicon
carbide, carbon black and silica, graphite; of which glass fiber,
silica, and calcium carbonate are preferred, calcium carbonate and
silica being particularly preferred because of their corrosion
prevention and lubricating properties. These inorganic fillers (d)
may be hollow, and two or more of them may be used in combination.
Furthermore, these inorganic fillers (d) may be subjected to
preliminary treatment with a coupling agent that comprises an
isocyanate-based compound, organic silane-based compound, organic
titanate-based compound, organic borane-based compound and epoxy
compound. In particular, calcium carbonate, silica, and carbon
black are preferred because they serve to enhance the corrosion
prevention, lubricating and conductive properties.
[0100] The content of these inorganic fillers should be 30 parts by
weight or less, preferably less than 10 parts by weight, more
preferably less than 1 part by weight, and still more preferably
0.8 part by weight or less, relative to the sum of said
polyphenylene sulfide resin (a) and said noncrystalline resin (b)
that accounts for 100 parts by weight. There are no requirements
for the minimum of the content, but it should preferably be 0.0001
part by weight or more. Addition of such inorganic fillers can
serve effectively to improve the elastic modulus of the material,
but the toughness will largely decrease if their content is larger
than 30 parts by weight. The content of said inorganic fillers may
be changed according to the balance between toughness and rigidity
required in the material.
(e) Other Additives
[0101] Moreover, the PPS resin composition may contain a resin
other than the polyetherimide resin and polyether sulfone resin
unless it has adverse influence on the effect of the invention.
Specifically, useful resins include olefin-based polymers and
copolymers that do not contain an epoxy group such as polyamide
resin, polybutylene terephthalate resin, polyethylene terephthalate
resin, modified polyphenylene ether resin, polysulfone resin,
polyallyl sulfone resin, polyketone resin, polyallylate resin,
liquid crystal polymer, polyether ketone resin, polythioether
ketone resin, polyether ether ketone resin, polyimide resin,
polyamide-imide resin, polytetrafluoroethylene resin, and
ethylene/butene copolymer.
[0102] Compounds as described below may also be added for property
modification. Thus, following ones may be added: plasticizers such
as polyalkylene oxide oligomer based compounds, thioether-based
compounds, ester-based compounds, and organic phosphorus based
compounds; crystal nucleating agents such as organic phosphorus
compounds and polyether ether ketone; metal soap such as montanic
acid wax, lithium stearate, and aluminum stearate; mold releasing
agents such as ethylene diamine/stearic acid/sebacic acid
condensation polymerization products and silicone-based compounds;
color protection agents such as hypophosphite; and other common
additives such as water, lubricant, ultraviolet ray protection
agents, coloring agents, and foaming agent. For any of the above
compounds, the content should preferably be 10 wt % or less, more
preferably 1 wt % or less, whereas a content of more than 20 wt %
relative to the entire composition will have an adverse influence
on the compound characteristics of the PPS resin (a).
Kneading Method
[0103] In a typical melting-kneading process, the PPS resin (a) is
fed to a generally known melting-kneading apparatus such as
uniaxial or biaxial extruder, Banbury mixer, kneader, and mixing
roll, and kneaded at a temperature +5 to 100.degree. C. above the
melting peak temperature. The use of a biaxial extruder, which can
exert a relatively shearing force, is preferred in order to achieve
fine dispersion of the polyetherimide resin and/or polyether
sulfone resin (b). Specifically, it is preferred to use a biaxial
extruder with a L/D (L: screw length, D: screw diameter) of 20 or
more that comprises two or more kneading units and knead the resin
at a screw rotation rate of 100 to 500 rotations/min at a mixing
temperature +10 to 70.degree. C. above the melting peak temperature
of the PPS resin (a). There are no specific limitations on the
order of material mixing during this process, and mixing may be
carried out by performing said melting-kneading process after
mixing all materials, first performing said melting-kneading
process after mixing some of the materials and subsequently another
melting-kneading process for the remaining materials, or first
mixing some of the materials and subsequently supplying the
remaining materials through a side feeder during melting-kneading
in a biaxial extruder. As a matter of course, major components may
be first kneaded as described above and then pelletized, followed
by addition of other minor additives immediately before
molding.
[0104] For the production of the PPS resin composition, it is
preferred, as described previously, to carry out the
melting-kneading process followed by carrying out the same
melting-kneading process subsequently one or more times in order
not only to decrease the alcohol generation from the melting of the
resulting resin composition but also to achieve finer dispersion of
the polyetherimide resin and/or polyether sulfone resin (b). There
are no specific limitations on the maximum number of repetition of
the kneading process, but it is preferred for the kneading to be
carried out once to three times more after the first implementation
of the melting-kneading process from the viewpoint of toughness
improvement and economic efficiency.
[0105] It is also possible that the amorphous resin selected from
the polyetherimide resin and/or polyether sulfone resin (b) is used
in a high content and that the polyphenylene sulfide resin (a) is
added during the repeated melting-kneading process carried out one
or more times after the first melting-kneading process to produce
the PPS resin composition so that the amorphous resin (b) is
diluted to an intended content. In this case, further additional
implementation of the kneading one or more times instead of the
dilution with the polyphenylene sulfide resin (a) is economically
preferred because this requires less kneading operation as compared
with the case where a PPS resin composition the same constitution
is produced. It is also possible that a polyphenylene sulfide resin
(a) with a different viscosity is added during the additional
melting-kneading process carried out one or more times in order to
control appropriately the flowability of the final PPS resin
composition to be produced.
[0106] It is more preferred to add 0.02 part by weight or more of
water during the melting-kneading process relative to the sum of
the PPS resin (a) and the polyetherimide resin and/or polyether
sulfone resin (b) that accounts for 100 parts by weight. If 0.02
part by weight or more of water is added, not only the alcohol
generation from the melting of the resulting resin composition is
decreased as described previously, but also the impurities
originating from the oligomers and by-products in the PPS resin
composition of the invention will be removed easily, leading to
improved moldability of the melt that is processed into film,
sheets, tubes, or other various moldings.
[0107] The volume of water to be added should preferably be 0.02
part by weight or more, more preferably 0.5 part by weight or more,
and still more preferably 1.0 part by weight or more. There are no
specific limitations on the maximum volume of water to be added,
but it should preferably be less than 5 parts by weight from the
viewpoint of the kneadability and the pressure increase in the
extruder due caused by water vapor.
[0108] There are no specific limitations on the timing of water
addition, but it is preferred to add water after the compound
containing at least one group selected from the epoxy group, amino
group and isocyanate group (c) has reacted with the polyphenylene
sulfide resin (a) or the noncrystalline resin (b), and, it is
particularly preferred to add water during the repeated
melting-kneading process carried out one or more times after the
first melting-kneading process. There are no specific limitations
on the way of adding water, but water may be side-fed in the middle
of the extruder using liquid feeding equipment such as gear pump
and plunger pump, or water may be added or side-fed in the middle
of the extruder during the repeated melting-kneading process
carried out one or more times following the first melting-kneading
process.
[0109] The polyphenylene sulfide resin composition is a resin
composition with a high toughness, but as a rough standard, it
should preferably have a tensile elongation of 80% or more, more
preferably 100% or more, when measured with a ASTM No. 4 dumbbell
specimen (using Tensilon UTA2.5T tensile tester with a chuck
distance of 64 mm and a tension speed of 10 mm/min).
[0110] The PPS resin composition has a very high toughness and has
a high processability because of smaller gas emission during
thermal melting, and therefore, it is particularly useful for
extrusion molding to produce film, sheets, and fiber as well as for
injection molding. Moreover, the PPS resin composition also has
barrier properties against automobile fuel as well as high
toughness. Therefore, it is useful to produce tubular extrusion
moldings, it is particular preferred as material to produce tubes
to transport automobile fuel. Such tubes may be preferably used to
produce multilayer tubes with the outer surface reinforced with a
PPS resin etc. with a different constitution. With such food
characteristics, it is suitable for producing general appliances,
pipes for automobiles, tubes, structures such as cases, metal
insert moldings for electric and electronic uses, electric
insulation film for motors, speaker diaphragms, and vapor-deposited
film for film capacitors.
[0111] A typical process to produce film through melt-processing of
the PPS resin composition is described below, but as a matter of
course, the disclosure is not limited to this process.
Specifically, pellets of the PPS resin composition are vacuum-dried
at 180.degree. C. for 3 hours or more, and then melted in an
extruder. Subsequently, it is passed through a filter and
discharged from the orifice of a T-die into a sheet. This sheet is
allowed to come in contact with a cooling drum for cooling and
solidification to provide a virtually non-oriented, unstretched
film.
[0112] The unstretched film is then biaxially orientated by biaxial
stretching. The stretching may be carried out by sequential biaxial
stretching, simultaneous biaxial stretching, or their
combination.
[0113] The biaxially stretched film is then heat-fixed while being
kept under tension or relaxed in the width direction, and cooled
down to room temperature while being relaxed if required, followed
by winding up to provide biaxially orientated film with a thickness
of 1 .mu.m to 150 .mu.m.
[0114] A typical process for processing the PPS resin composition
to produce a multilayer tube is described below, though as a matter
of course, the invention is not limited to this process.
Specifically, one of the useful methods is a co-extrusion process
in which molten resin is supplied from an extruder into a tubular
die and extruded into a multilayer tube.
EXAMPLES
[0115] Representative examples are described more specifically
below.
[0116] The material characteristics used in the examples given
below were determined by the following methods.
[Injection Molding (1st Time)]
[0117] A Sumitomo-Netstal SG75 injection molding machine is used
under the conditions of a resin temperature of 310.degree. C. and a
die temperature of 150.degree. C. to provide an ASTM No. 4 dumbbell
specimen.
[Injection Molding (2nd Time)]
[0118] The ASTM No. 4 dumbbell specimen obtained from the first
injection molding was crushed in a crusher into rectangular pieces
of about 1 to 5 mm. These pieces were processed with a
Sumitomo-Netstal SG75 injection molding machine under the
conditions of a resin temperature of 310.degree. C. and a die
temperature of 150.degree. C. to provide an ASTM No. 4 dumbbell
specimen.
[Tensile Test]
[0119] Measurements were made with a Tensilon UTA2.5T tensile
tester under the conditions of a chuck distance 64 mm and a tension
speed of 10 mm/min. The specimen obtained from the first injection
molding was used for the test.
[Morphological Observation]
[0120] A central portion of the ASTM No. 4 dumbbell specimen is cut
in the direction perpendicular to the flow of the resin, and a thin
specimen of 0.1 .mu.m or less is cut out at -20.degree. C. from the
central region of its cross section, followed by measurement of the
diameter of the dispersed particles at a magnification of 10,000 to
20,000 under a Hitachi, Ltd., H-7100 transmission electron
microscope (resolution (particle image) 0.38 nm, magnifying power
500,000 to 600,000).
[Alcohol Generation]
[0121] A 3 g amount of PPS resin composition pellets dried
overnight in hot air of 130.degree. C. is weighed into a glass
ampule consisting of a body portion of 100 mm.times.25 mm and a
neck portion of 255 mm.times.12 mm, both with a thickness of 1 mm,
and then vacuum-encapsulated. Only the body portion of the ampule
was inserted into a ceramic tubular electric furnace ARF-30K
manufactured by Asahi Rika-Manufacturing) and heated at 350.degree.
C. for 30 minutes. After taking out the ampule, the neck portion of
the ampule that was not heated by the tubular furnace and contained
liquefied volatile gas was cut out with a file. Then the liquefied
gas was recovered by dissolving it in 4 g of NMP, and the volume of
alcohol was determined by using a Shimadzu Corporation GC-14A gas
chromatograph.
[Evaluation of Film Production Performance]
[0122] The amount of gas generated and liquefied near the orifice
during the film production, and the resulting film breakage was
observed, and evaluation was conducted according to the following
criteria. [0123] A: Gas generation and liquefaction is hardly seen
near the orifice after 24 hours of film production, and film
breakage is not found. [0124] B: Some degree of gas generation and
liquefaction is seen near the orifice after 24 hours of film
production, and but film breakage is not found. [0125] C: A
considerable degree of gas generation and liquefaction is seen near
the orifice after several hours of film production, and film
breakage takes place frequently, requiring cleaning of the orifice
to continue the film production.
Reference Example 1
Polymerization of PPS Resin (a)
PPS-1
[0126] In a 70-liter autoclave equipped with a stirrer, 8,267.37 g
(70.00 moles) of 47.5% sodium hydrosulfide, 2,957.21 g (70.97
moles) of 96% sodium hydroxide, 11,434.50 g (115.50 moles) of
N-methyl-2-pyrolidone (NMP), 2,583.00 g (31.50 moles) of sodium
acetate, and 10,500 g of ion-exchanged water were fed and gradually
heated for about 3 hours up to 245.degree. C. under atmospheric
pressure while supplying nitrogen to evaporate 14,780.1 g of water
and 280 g of NMP, followed by cooling the reaction container to
160.degree. C. The residual water content per mole of the alkali
metal sulfide fed was 1.06 moles including the water consumed to
hydrolyze the NMP. The fly loss of the hydrogen sulfide was 0.02
mole per mole of the alkali metal sulfide fed.
[0127] Subsequently, 10,235.46 g (69.63 moles) of p-dichlorobenzene
and 9,009.00 g (91.00 moles) of NMP were added, and the reaction
container was sealed in a nitrogen atmosphere and heated at a rate
of 0.6.degree. C./min up to 23.8.degree. C. while stirring at 240
rpm. After allowing the reaction to proceed at 238.degree. C. for
95 minutes, the reaction container was heated at a rate of
0.8.degree. C./min up to 270.degree. C. After allowing the reaction
to proceed at 270.degree. C. for 100 minutes, the reaction
container was cooled at a rate of 1.3.degree. C./min down to
250.degree. C. while injecting 1,260 g (70 moles) of water, this
process being completed in 15 minutes. Then, it was cooled at rate
of 1.0.degree. C./min down to 200.degree. C., followed by rapid
cooling down to near room temperature.
[0128] The contents were taken out and diluted with 26,300 g of
NMP, and the solvent and the solid material were passed through a
filter (80 mesh) to obtain particles, which was washed in 31,900 g
of NMP. The particles were washed several times in 56,000 g of
ion-exchanged water and filtered, they were washed again in 70,000
g of 0.05 wt % acetic acid aqueous solution and filtered. They were
washed in 70,000 g of ion-exchanged water and filtered, and the
resulting water-containing PPS particles were dried in hot air at
80.degree. C. and further dried under reduced pressure at
120.degree. C. The resulting PPS had a melt viscosity of 200 Pas
(at 310.degree. C., shear velocity 1000/s).
Reference Example 2
Polymerization of PPS Resin (a)
PPS-2
[0129] In a 70-liter autoclave equipped with a stirrer, 8,267.37 g
(70.00 moles) of 47.5% sodium hydrosulfide, 2,957.21 g (70.97
moles) of 96% sodium hydroxide, 11,434.50 g (115.50 moles) of
N-methyl-2-pyrolidone (NMP), 861.00 g (10.5 moles) of sodium
acetate, and 10,500 g of ion-exchanged water were fed and gradually
heated for about 3 hours up to 245.degree. C. under atmospheric
pressure while supplying nitrogen to evaporate 14,780.1 g of water
and 280 g of NMP, followed by cooling the reaction container to
160.degree. C. The residual water content per mole of the alkali
metal sulfide fed was 1.06 moles including the water consumed to
hydrolyze the NMP. The fly loss of the hydrogen sulfide was 0.02
mole per mole of the alkali metal sulfide fed.
[0130] Subsequently, 10,235.46 g (69.63 moles) of p-dichlorobenzene
and 9,009.00 g (91.00 moles) of NMP were added, and the reaction
container was sealed in a nitrogen atmosphere and heated at a rate
of 0.6.degree. C./min up to 238.degree. C. while stirring at 240
rpm. After allowing the reaction to proceed at 238.degree. C. for
95 minutes, the reaction container was heated at a rate of
0.8.degree. C./min up to 270.degree. C. After allowing the reaction
to proceed at 270.degree. C. for 100 minutes, the reaction
container was cooled at a rate of 1.3.degree. C./min down to
250.degree. C. while injecting 1,260 g (70 moles) of water, this
process being completed in 15 minutes. Then, it was cooled at rate
of 1.0.degree. C./min down to 200.degree. C., followed by rapid
cooling down to near room temperature.
[0131] The contents were taken out and diluted with 26,300 g of
NMP, and the solvent and the solid material were passed through a
filter (80 mesh) to obtain particles, which was washed in 31,900 g
of NMP. The particles were washed several times in 56,000 g of
ion-exchanged water and filtered, they were washed again in 70,000
g of 0.05 wt % acetic acid aqueous solution and filtered. They were
washed in 70,000 g of ion-exchanged water and filtered, and the
resulting water-containing PPS particles were dried in hot air at
80.degree. C. and further dried under reduced pressure at
120.degree. C. The resulting PPS resin (a) had a melt viscosity of
60 Pas (at 310.degree. C., shear velocity 1000/s).
Reference Example 3
Polymerization of PPS Resin (a)
PPS-3
[0132] In a 70-liter autoclave equipped with a stirrer, 8,267.37 g
(70.00 moles) of 47.5% sodium hydrosulfide, 2,957.21 g (70.97
moles) of 96% sodium hydroxide, 11,434.50 g (115.50 moles) of
N-methyl-2-pyrolidone (NMP), 1,639.99 g (20.0 moles) of sodium
acetate, and 10,500 g of ion-exchanged water were fed and gradually
heated for about 3 hours up to 245.degree. C. under atmospheric
pressure while supplying nitrogen to evaporate 14,780.1 g of water
and 280 g of NMP, followed by cooling the reaction container to
160.degree. C. The residual water content per mole of the alkali
metal sulfide fed was 1.06 moles including the water consumed to
hydrolyze the NMP. The fly loss of the hydrogen sulfide was 0.02
mole per mole of the alkali metal sulfide fed.
[0133] Subsequently, 10,235.46 g (69.63 moles) of p-dichlorobenzene
and 9,009.00 g (91.00 moles) of NMP were added, and the reaction
container was sealed in a nitrogen atmosphere and heated at a rate
of 0.6.degree. C./min up to 238.degree. C. while stirring at 240
rpm. After allowing the reaction to proceed at 238.degree. C. for
95 minutes, the reaction container was heated at a rate of
0.8.degree. C./min up to 270.degree. C. After allowing the reaction
to proceed at 270.degree. C. for 100 minutes, the reaction
container was cooled at a rate of 1.3.degree. C./min down to
0.250.degree. C. while injecting 1,260 g (70 moles) of water, this
process being completed in 15 minutes. Then, it was cooled at rate
of 1.0.degree. C./min down to 200.degree. C., followed by rapid
cooling down to near room temperature.
[0134] The contents were taken out and diluted with 26,300 g of
NMP, and the solvent and the solid material were passed through a
filter (80 mesh) to obtain particles, which was washed in 31,900 g
of NMP. The particles were washed several times in 56,000 g of
ion-exchanged water and filtered, they were washed again in 70,000
g of 0.05 wt % acetic acid aqueous solution and filtered. They were
washed in 70,000 g of ion-exchanged water and filtered, and the
resulting water-containing PPS particles were dried in hot air at
80.degree. C. and further dried under reduced pressure at
120.degree. C. The resulting PPS resin (a) had a melt viscosity of
130 Pas (at 310.degree. C., shear velocity 1000/s).
Reference Example 4
[0135] Polyetherimide (PEI): Ultem 1010, manufactured by GE [0136]
Polyether sulfone (PES): Sumikaexcel 3600G, manufactured by
Sumitomo Chemical Co., Ltd.
Examples 1 to 12
[0137] The components given in Tables 1 and 2 were dry-blended
according to the proportions shown in Tables 1 and 2, and
melt-kneaded in a Japan Steel Works TEX 30.alpha. biaxial extruder
(L/D=45.5, kneading at 5 positions) with a vacuum bent under the
conditions of a screw rotation rate of 300 rpm and a cylinder
temperature adjusted so as to give resin of a temperature of
330.degree. C. at the orifice of the die. The resin was pelletized
with a strand cutter. After being dried overnight at 130.degree.
C., the pellets were injection-molded, and the tensile breaking
elongation of each molded specimen and the diameter of the
dispersed particles in the island phase were measured. Pellets
dried overnight at 130.degree. C. were also used for measuring the
alcohol generation.
[0138] Furthermore, pellets dried at 180.degree. C. for 3 hours
under a reduced pressure of 1 mmHg were supplied to an extruder,
melted at 310.degree. C., passed through a metal-fiber filter with
a 95% cut diameter of 10 .mu.m, and discharged through the orifice
of a T-die at a discharge rate of 50 kg/hr. The extruded molten
sheet was cooled and solidified by allowing it to come in close
contact with a metal drum with its surface maintained at 25.degree.
C. by applying positive electricity to produce a sheet of a
non-oriented polyphenylene sulfide resin composition. Then, this
unstretched sheet was subjected to a longitudinal drawing machine
consisting of two or more heated rolls, in which the difference in
their circumferential speed served to stretch the sheet 3.5 times
in the longitudinal direction at a temperature of 103.degree. C.
Subsequently, both edges of the film sheet was held with clips,
introduced into a tenter where the film was stretched 3.5 times in
the width direction at a temperature of 105.degree. C., followed by
heat treatment at a temperature of 260.degree. C. for 2 seconds to
produce biaxially orientated polyphenylene sulfide resin
composition film with a thickness of 25 .mu.m. Results are shown in
Tables 1 and 2.
Example 13
[0139] The components given in Column "example 13" in Table 2 were
dry-blended according to the proportions shown in Column "example
13" in Table 2, and melt-kneaded in a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 5 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die. The resin
was pelletized with a strand cutter. Then, for molded specimens of
these pellets, the tensile breaking elongation, the diameter of the
dispersed particles in the island phase, and the alcohol generation
were measured by the same procedure as in Example 2. Results are
shown in Table 2.
Example 14
[0140] Melt-kneading was carried out by the same procedure as in
Example 2 except that material was prepared by dry-blending the
components given in Column "Example 14" in Table 2 according to the
proportions shown in Column "Example 14" in Table 2, and that
kneading was performed at 3 positions in the biaxial extruder.
Then, the tensile breaking elongation, the diameter of the
dispersed particles in the island phase, and the alcohol generation
were measured, and the film production performance was evaluated.
Results are shown in Table 2.
Example 15
[0141] The components given in Column "Example 15" in Table 2 were
dry-blended according to the proportions shown in Column "Example
15" in Table 2, and melt-kneaded in a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 3 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die. The resin
was pelletized with a strand cutter. Then, these pellets were
melt-kneaded again under the same conditions as described above,
and pelletized with a strand cutter. By the same procedure as in
Example 2 except for this, the tensile breaking elongation, the
diameter of the dispersed particles in the island phase, and the
alcohol generation were measured, and the film production
performance was evaluated. Results are shown in Table 2.
Example 16
[0142] The components given in Column "Example 15" in Table 2 were
dry-blended according to the proportions shown in Column "Example
15" in Table 2, and melt-kneaded in a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 3 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die. The resin
was pelletized with a strand cutter. Then, water was added to the
pellets so that the components given in Column "Example 16" in
Table 2 account for the same proportions as in Column "Example 16"
in Table 2, and the pellets were melt-kneaded under the same
conditions as described above, and pelletized with a strand cutter.
By the same procedure as in Example 2 except for this, the tensile
breaking elongation, the diameter of the dispersed particles in the
island phase, and the alcohol generation were measured, and the
film production performance was evaluated. Results are shown in
Table 2.
Example 17
[0143] The components given in Column "Example 9" in Table 1 were
dry-blended according to the proportions shown in Column "Example
9" in Table 1, and melt-kneaded in a Japan Steel Works TEX
30.alpha. biaxial extruder (LID=45.5, kneading at 3 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die. The resin
was pelletized with a strand cutter. Then, PPS-1 and water were
added to the pellets so that the components given in Column
"Example 17" in Table 2 account for the same proportions as in
Column "Example 17" in Table 2, and the pellets were melt-kneaded
under the same conditions as described above, and pelletized with a
strand cutter. By the same procedure as in Example 2 except for
this, the tensile breaking elongation, the diameter of the
dispersed particles in the island phase, and the alcohol generation
were measured, and the film production performance was evaluated.
Results are shown in Table 2.
Comparative Example 1
[0144] Melt kneading was carried out using a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 5 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die as shown in
Table 1 by the same procedure as in Example 1 except that the PEI
and/or PES (b) and the compound comprising isocyanate group, epoxy
group and/or amino group (c) were not used. The resin was
pelletized with a strand cutter. After being dried overnight at
130.degree. C., the pellets were injection-molded, the tensile
breaking elongation of the molded specimens was measured, and the
film production performance was evaluated. As seen from Table 1,
results show that the tensile elongation was extremely lower than
in Example 2.
Comparative Example 2
[0145] Melt kneading was carried out using a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 5 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die as shown in
Table 1 by the same procedure as in Example 1 except that the
compound comprising isocyanate group, epoxy group and/or amino
group (c) was not used. The resin was pelletized with a strand
cutter. After being dried overnight at 130.degree. C., the pellets
were injection-molded, and the tensile breaking elongation of the
molded specimens and the diameter of the dispersed particles in the
island phase were measured. Then, the film production performance
was evaluated. As seen from Table 1, results show that the tensile
elongation is extremely lower than in Examples 1 through 2 and 5
through 7. It is also seen that the diameter of the dispersed
particles in the island phase for the first mold injection is
large, and that for the second mold injection is still larger.
Comparative Example 3
[0146] The same evaluation procedures as in Example 2 were carried
out except that melt-kneading was carried out using a Tanabe
Plastics Machinery 40 mm-diameter uniaxial extruder with a vacuum
bent under the conditions of a preset temperature of 300.degree. C.
and a screw rotation rate of 80 rpm. Results are shown in Table 1.
The tensile elongation is lower and the dispersed particle diameter
in the island phase is larger than in Example 2. Furthermore, the
alcohol generation is larger than in Example 2, and frequent film
breakage is seen during film production.
Comparative Examples 4 and 5
[0147] Melt kneading was carried out using a Japan Steel Works TEX
30.alpha. biaxial extruder (L/D=45.5, kneading at 5 positions) with
a vacuum bent under the conditions of a screw rotation rate of 300
rpm and a cylinder temperature adjusted so as to give resin of a
temperature of 330.degree. C. at the orifice of the die as shown in
Table 1 by the same procedure as in Examples 10 and 11 except that
the compatibilizer (c) was not used. The resin was pelletized with
a strand cutter. After being dried overnight at 130.degree. C., the
pellets were injection-molded, and the tensile breaking elongation
of the molded specimens and the diameter of the dispersed particles
in the island phase were measured. Pellets dried overnight at
130.degree. C. were also used for measuring the alcohol generation,
and the film production performance was evaluated. As seen from
Table 2, results show that the tensile elongation is extremely
lower than in Examples 10 and 11. It is also seen that the diameter
of the dispersed particles in the island phase for the first mold
injection is large, and that for the second mold injection is still
larger.
TABLE-US-00001 TABLE 1 Comparative Comparative Comparative example
1 example 2 example 3 Example 1 Example 2 Example 3 Type of PPS
PPS-1 PPS-1 PPS-1 PPS-1 PPS-1 PPS-2 Amount of PPS wt % 100 95 95 95
95 95 Type of PEI, PES -- PEI PEI PEI PEI PEI Amount of PEI, PES wt
% -- 5 5 5 5 5 Type of compatibilizer -- -- C-2 C-1 C-2 C-2 Amount
of compatibilizer parts by -- -- 0.5 0.5 0.5 0.5 weight*) Type of
inorganic filler -- -- -- -- -- -- Amount of inorganic filler parts
by -- -- -- -- -- -- weight*) Extruder biaxial biaxial uniaxial
biaxial biaxial biaxial L/D***) 45.5 45.5 33 45.5 45.5 45.5
Positions of kneading 5 5 0 5 5 5 Tesile breaking elongation % 30
25 60 140 150 120 PEI, PES dispersed particle diameter nm -- 2500
1200 500 200 400 (1st injection molding) PEI, PES dispersed
particle diameter nm -- 3400 1300 550 200 400 (2nd injection
molding) Repetition of kneading times 1 1 1 1 1 1 Water content
parts by -- -- -- -- -- -- weight*) Alcohol generation mmol %**) --
-- 0.98 -- 0.35 0.37 Film production performance B B C B B B
Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Type of
PPS PPS-3 PPS-1 PPS-1 PPS-1 PPS-1 PPS-1 Amount of PPS wt % 95 95 95
95 95 70 Type of PEI, PES PEI PEI PEI PEI PES PEI Amount of PEI,
PES wt % 5 5 5 5 5 30 Type of compatibilizer C-2 C-3 C-4 C-5 C-2
C-2 Amount of compatibilizer parts by 0.5 0.5 0.5 0.5 0.5 1.5
weight*) Type of inorganic filler -- -- -- -- -- -- Amount of
inorganic filler parts by -- -- -- -- -- -- weight*) Extruder
biaxial biaxial biaxial biaxial biaxial biaxial L/D***) 45.5 45.5
45.5 45.5 45.5 45.5 Positions of kneading 5 5 5 5 5 5 Tesile
breaking elongation % 130 125 120 80 160 110 PEI, PES dispersed
particle diameter nm 300 450 500 800 180 300 (1st injection
molding) PEI, PES dispersed particle diameter nm 300 450 500 900
180 300 (2nd injection molding) Repetition of kneading times 1 1 1
1 1 1 Water content parts by -- -- -- -- -- -- weight*) Alcohol
generation mmol %**) 0.35 -- 0.41 0.43 0.36 0.55 Film production
performance B B B B B B *)Sum of PPS and (PEI, PES) accounts for
100 parts by weight. **)Alcohol generation in mmol % per gram of
PPS resin composition. ***)Ratio of extruder's screw length (L) to
screw diameter (D) C-1: 2,6-tolylene diisocyanate (Nippon
Polyurethane Industry Co., Ltd.; Coronate T-65) C-2:
3-isocyanatepropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.;
KBE9007) C-3: novolak phenol epoxy (Sumitomo Chemical Co., Ltd.;
ESCN-220HH) C-4: 2-(3,4-epoxy cyclohexyl)ethyl
trimethoxysilane(Shin-Etsu Chemical Co., Ltd.; KBM303) C-5:
gamma-aminopropyl triethoxysilane (Shin-Etsu Chemical Co., Ltd.;
KBE903) D-1: calcium carbonate (Calfine Co., Ltd.; KSS-1000)
TABLE-US-00002 TABLE 2 Comparative Example 10 Example 11 Example 12
Example 13 example 4 Type of PPS PPS-1 PPS-1 PPS-1 PPS-1 PPS-1
Amount of PPS wt % 90 95 95 95 95 Type of PEI, PES PEI PEI PEI PEI
PEI Amount of PEI, PES wt % 10 5 5 5 5 Type of compatibilizer C-2
C-2 C-2 C-2 -- Amount of compatibilizer parts by 1 0.5 0.5 0.5 --
weight*) Type of inorganic filler -- D-1 D-1 D-1 D-1 Amount of
inorganic filler parts by -- 0.5 8 40 0.5 weight*) Extruder biaxial
biaxial biaxial biaxial biaxial L/D***) 45.5 45.5 45.5 45.5 45.5
Positions of kneading 5 5 5 5 5 Tesile breaking elongation % 165
145 100 15 75 PEI, PES dispersed particle diameter nm 150 210 195
195 1100 (1st injection molding) PEI, PES dispersed particle
diameter nm 150 210 195 195 2200 (2nd injection molding) Repetition
of kneading times 1 1 1 1 1 Water content parts by -- -- -- -- --
weight*) Alcohol generation mmol %**) 0.44 0.38 0.35 0.29 -- Film
production performance B B B -- B Comparative example 5 Example 14
Example 15 Example 16 Example 17 Type of PPS PPS-1 PPS-1 PPS-1
PPS-1 PPS-1 Amount of PPS wt % 95 90 90 90 90 Type of PEI, PES PEI
PEI PEI PEI PEI Amount of PEI, PES wt % 5 10 10 10 10 Type of
compatibilizer -- C-2 C-2 C-2 C-2 Amount of compatibilizer parts by
-- 0.5 0.5 0.5 0.5 weight*) Type of inorganic filler D-1 -- -- --
-- Amount of inorganic filler parts by 8 -- -- -- -- weight*)
Extruder biaxial biaxial biaxial biaxial biaxial L/D***) 45.5 45.5
45.5 45.5 45.5 Positions of kneading 5 3 3 3 3 Tesile breaking
elongation % 35 135 160 170 165 PEI, PES dispersed particle
diameter nm 1300 250 135 120 125 (1st injection molding) PEI, PES
dispersed particle diameter nm 2300 250 135 120 125 (2nd injection
molding) Repetition of kneading times 1 1 2 2 2 Water content parts
by -- -- -- 1 1 weight*) Alcohol generation mmol %**) -- 0.65 0.26
0.15 0.16 Film production performance B C A A A *)Sum of PPS and
(PEI, PES) accounts for 100 parts by weight. **)Alcohol generation
in mmol % per gram of PPS resin composition. ***)Ratio of
extruder's screw length (L) to screw diameter (D) C-1: 2,6-tolylene
diisocyanate (Nippon Polyurethane Industry Co., Ltd.; Coronate
T-65) C-2: 3-isocyanatepropyltriethoxysilane (Shin-Etsu Chemical
Co., Ltd.; KBE9007) C-3: novolak phenol epoxy (Sumitomo Chemical
Co., Ltd.; ESCN-220HH) C-4: 2-(3,4-epoxy cyclohexyl)ethyl
trimethoxysilane(Shin-Etsu Chemical Co., Ltd.; KBM303) C-5:
gamma-aminopropyl triethoxysilane (Shin-Etsu Chemical Co., Ltd.;
KBE903) D-1: calcium carbonate (Calfine Co., Ltd.; KSS-1000)
Example 18
[0148] The composition used in Example 10 was supplied to a 65 mm
uniaxial extruder, and the discharged resin was collected through
an adapter and extruded from a die to produce a tube. Then, the
tube was cooled and passed through a sizing die, which serves for
size control, followed by taking up the material from a take-up
apparatus at a rate of 50 cm/min to provide a high-toughness tube
with an outside diameter of 8 mm and an inside diameter of 6
mm.
INDUSTRIAL APPLICABILITY
[0149] The PPS resin composition has a very high toughness and has
a high processability because of smaller gas emission during
thermal melting, and therefore, it is particularly useful for
extrusion molding to produce film, sheets, and fiber as well as for
injection molding.
* * * * *